Gases

Our first look at large collections of particles acting together!

Gases & Atoms First

The simplest model of a gas has all the molecules moving and acting independently. But, with a large number of particles, their average behavior is strictly delineated. Only He, Ne, Ar, Kr, Xe, and Rn are atomic gases. Really, we are looking at a particles-first approach here!

Basic Ideas of This Chapter

We present the ideal gas first.
Gas molecules move independently. Forces between molecules are nil. Model seems very simple but it explains a great deal!

We shall end with a description of real gases.

Some intermolecular forces enter in. Structural effects (in terms of size) of molecules also enter into our discussions.

Studying the Behavior of Substances

To give a more general perspective, there are certain things we can measure that lead to understanding the state of a system. A short list:
Pressure (P) Volume (V) Temperature (T) Amount of substance (mass or moles, w or n) Composition (for mixtures; notation later)

A Little Analysis
The properties listed on the previous slide are what we could call observables. One thing we try to do in science is connect observables together if possible. Ideally, we can get an equation of state. Having the equation of state, we then try to go further and explain it in terms of individual particles. That is one of the main things we shall do in this chapter.

Our First Physical Property: P

P stands for pressure. Pressure = force/unit area On the average, you have 14.7 lb of air above you. This exerts the same pressure on you from all sides! Why? (We explain this verbally.)

Here is the explanation!

Pressure is caused by particles (molecules) hitting you. When a molecule bounces off you, its change of momentum is the force exerted. An equal number is hitting you from all sides! Pressure is thus isotropic.

Needless to say, the more particles, the higher the pressure!

Units of Pressure
We usually think of pressure in terms of standard atmospheric pressure. The SI unit of pressure is the pascal (Pa). This is 1 Pa = 1 N/m2. 1 atm 101325 Pa (exactly!) The next slide shows some standard pressure units. Ones with exact defintions are marked with an asterisk (*).

Some Pressure Units

Unit Pascal Pounds/in2 Torr (mm Hg) Bar Inches of mercury Atmosphere Abbreviation Pa (= 1 N/m2) psi (or ) torr bar in Hg atm Std. Atmospheric Pressure 101325 Pa (*) 14.6959488 psi 760 torr (*) 1.01325 bar (*) 29.9212598 1 atm (*)

Measuring Pressure
Various instruments are used nowadays. For measuring air pressure, the traditional instrument is the mercury barometer.

Measuring Gas Pressures

Pressures are measured by manometers. Some of these are mechanical but the traditional instruments use columns of Hg. At the right is an openended manometer. Note that we have to correct for atmospheric pressure!

Other types of Manometers

Simple Closed-End Manometer A McLeod Gauge (Low Pressures)

We now look at some gas laws.

Remember our observable variables:
n, P, V, and T

For the various laws, we keep two of these constant and note how the remaining two are related. We examine these in the next few slides...

Boyles Law
T and n held constant. V is inversely proportional to P. Or, PV = constant. Boyle is watching us to the right!

A Depiction of Boyles Experiment

For a gas subject to Boyles Law...

Charless Law
Here, we hold n and P constant and observe V vs. T. VT V = (const) T Needless to say, Charles very much approves of us using his work!

Here we see the experimental results!

Note the intercept!

All gases extrapolate to the same point. This is -273.15C. This is also 0.00 K. In other words, this is the first place that the concept of absolute zero appears. T(K) = T(C) + 273.15

For a gas subject to Charles Law...

We see something similar for P.

If V and n are held constant, we can look at P vs. T. P T. Or, P = (const) T. This the law of GayLussac (not mentioned in book). Gay-Lussac...

Pour Monsieur Gay-Lussac...

Avogadros Law
Here, we hold P and T constant and observe V vs. n. This is really where the concept of the mole was first proposed. Credit for this goes to Avogadro... ...who, of course, is also watching us!

Avogadros Law is also a simple graph...

For a gas obeying Avogadros Law...

Here are the 3 laws as in the book...

These can be combined to give...

We make this an equation by putting in a constant...

How the text looks at this...

Another view of the constant...

Values of R

Note these exact conversion factors...

We can exploit this sometimes to get a combined gas law (verbal discussion)...

We write the combined gas law on the board...

We look at how this handles the following
Boyles Law case... Charles Law case... Avogadros Law case... Single gas sample at different P, V, and T (same n)

In all this...
Watch your units! We especially need to watch R! Also, how do we best handle changes in pressure, temperature, and energy units. We shall now discuss some of these topics!

We have two definitions of the mole we shall be using...

How many particles in a mole?

NA = 6.0221415

23 10

-1 mol

Some Delightful Applications!

I. Molar Volume II. Gas Density III. Molar Mass (molecular weight) of a Gas

Molar Volume

Special Condition: STP

STP means standard temperature at pressure P = 1 atm (exactly) T = 0.00C = 273.15K Under these conditions, V = 22.4L for all ideal gases!

A More Precise Calculation (n = 1)

All Ideal Gases the Same! (AIGATS!)

Density: General Definition pHirst!

density = mass/volume Units:
g/L (gases) g/mL (liquids & solids) kg/m3 (SI unit)

Density of a gas...

Molar Mass of a Gas

This is important! This is a method of determining molar mass (aka molecular weight) The equation is to the right...

Gas Mixtures & Partial Pressures

Ideal gases in a mixture exert their pressures independently. This is called Daltons Law of Partial Pressures. We show some math in the next slide...

Look at a mixture of gases A, B, C, & D

This leads to a concentration unit, mole fraction (for a given gas, i )

Useful Relations...

Collecting Gases over Water

A common method of collecting gaseous products of reactions. Works well as long as the gas is not soluble in water! This is the first time that we encounter vapor pressure.

Yes, water is a liquid but...

Example: Collecting H2 over water

Gas Stoichiometry
Before we get started on this, please remember that we have two definitions for a mole: In terms of mass. In terms of the ideal gas law.

A Thank You to John Dalton!

In his prime!
After too much pHun with gases!

Shortcut Method for Stoichiometry

1) Write the balanced chemical equation. 2) Place the relevant coefficients below the equation. 3) Place the relevant number of moles above the equation. 4) Construct the needed equation from ratios. 5) Solve this equation for whatever you are looking for (pressure, moles, mass, volume, etc.)

A Picture of the Shortcut Method

Comparing Moles via Ratios

An Abstract Example
How many grams of B are needed to produce V mL of a gas, C, at a given P and T? The way to set this up is shown to the right.

Two ways to do these problems!

I. Write the balanced chemical equation (BCE) and construct the algebraic solution for a given problem by use of ratios. II. Use conversion factors as shown in the book.

The Kinetic Theory of Gases

This is a very simple model. But it gives a lot of profound conclusions. Coupled with quantum mechanics, it actually predicts the ideal gas law. We shall skip the QM however! And look at other things more relevant to us!

Some Postulates...
I. The size of gas particles is negligibly small. II. The average kinetic energy of a particle is proportional to the temperature (in K). III. All collisions between particles and with the walls of the container are completely elastic.

pHun with equations!

pHun (continued)...

pHun (it goes on!)...

pHeeling the Pressure?

Remember the 2nd Postulate?

Lets put it in!

And...................

pHinally, putting in THE constant gives...

Lets Look at a Gas in Action...

Time to Call in Some Mechanics!

Major Point!

In a gas at a given temperature, lighter particles travel faster (on average) than do heavier ones! BUT, all have the same (average) kinetic energy!

Remember...

Root Mean Square Velocity

To make sense of this, we need the MOLE!

Some Razzle-Dazzle Math!

pHinal Equation for RMS Speed...

Watch your units here!!!

R = 8.314472 J/molK MSI is in kg/mol (!)
(This is the SI unit for MW)

T is in Kelvins.

Example: Nitrogen gas (N2) at 25.00C

Example: He gas at 25.00C

For Sake of Completeness...

Average Velocity Most Probable Velocity

A Comparison...

A Graphical View

And another view...

Two Processes to Look At Now

Diffusion This is the process whereby two gases mix. Basically, the molecules mix while colliding. This is influenced by the mean free path (discussed shortly). Effusion This is the rate of escape of molecules through a pin hole into a vacuum. How this (and diffusion) are handled by kinetic theory is shown in the next slide.

One Picture of Diffusion...

And another (dj vu?)...

A Picture of Effusion

Both Processes Follow Grahams Law

The rate of effusion (diffusion) is inversely proportional to the square root of the molar mass. Derivation on next slide. In the meantime, meet Thomas Graham!

A Short Derivation

Mean Free Path

Until now, we have been ignoring molecular size. But molecules do collide and do have size. The distance a molecule travels between collisions is called the mean free path.

An Equation for Mean Free Path ()

is the molecular collision diameter in m. P is the pressure in pascals. R is in J/molK. This is just a bonus equation and will not be on exams!

Example: Mean free path in O2

We shall assume STP. The molecular diameter of O2 is 361 pm. We shall analyze the units on the board. (Under the conditions of this problem, O2 travels about 180 molecular diameters before colliding.)

A Bonus: The Speed of Sound

Monatomic Gas Diatomic Gas

Examples (25.00C)
Helium Nitrogen

Real Gases
These differ from ideal gases in the following ways:
Real molecules are not pointsthey have size. There are attractive forces between the molecules.

Conditions for a gas to behave like an ideal gas...

High temperature (explain why!) Low pressure (again, explain this!)

Experimental Molar Volumes (STP)

We look at Ar and pressure...

Correcting for Molecular Volume

Ideal Gas Volume Correction

We look at Xe and Pressure...

Correcting Pressure for Effects of Intermolecular Forces

Ideal Behavior Pressure Correction

Multiplying the Corrected Values Together Gives the van der Waals Equation

If n = 1, this takes on a simpler form! (Vm is the molar volume.)

This is a semi-empirical equation...

The form of the equation comes from good physical arguments. But, a and b must be obtained experimentally. A table of these is to the right...

A little chalk talk...

The vdw equation is an equation of state for real gases. It is about the simplest one that works well. But, it is not perfect! There are many other equations! As you can see, van der Waals was proud of it!

Another view of real gas behavior

Z = PV/RT is called the compressibility factor of a gas. Z = 1 for an ideal gas. Real gases are much more interesting! See the slide to the right (gases at 273K)...

The End of Gases!

Yes, that is enough!